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In our review, we have presented a summary of the research accomplishments of nanostructured multimetal-based electrocatalysts synthesized by modified polyol methods, especially the special case of Pt-based nanoparticles associated with increasing potential applications for batteries, capacitors, and fuel cells. To address the problems raised in serious environmental pollution, disease, health, and energy shortages, we discuss and present an improved polyol process used to synthesize nanoparticles from Pt metal to Pt-based bimetal, and Pt-based multimetal catalysts in the various forms of alloy and shell core nanostructures by practical experience, experimental skills, and the evidences from the designed polyol processes. In their prospects, there are the micro/nanostructured variants of hybrid Pt/nanomaterials, typically such as Pt/ABO3-type perovskite, Pt/AB2O4-type ferrite, Pt/CoFe2O4, Pt/oxide, or Pt/ceramic by modified polyol processes for the development of electrocatalysis and energy technology. In the future, we suggest that both the polyol and the sol-gel processes of diversity and originality, and with the use of various kinds of water, alcohols, polyols, other solvents, reducing agents, long-term capping and stabilizing agents, and structure- and property-controlling agents, are very effectively used in the controlled synthesis of micro/nanoparticles and micro/nanomaterials. It is understood that at the levels of controlling and modifying molecules, ions, atoms, and nano/microscales, the polyol or sol-gel processes, and their technologies are effectively combined in bottom-up and top-down approaches, as are the simplest synthetic methods of physics, chemistry, and biology from the most common aqueous solutions as well as possible experimental conditions.

Compressive surface strains have been necessary to boost oxygen reduction reaction (ORR) activity in core/shell M/platinum (Pt) catalysts (where M can be nickel, cobalt, or iron). We report on a class of platinum-lead/platinum (PtPb/Pt) core/shell nanoplate catalysts that exhibit large biaxial strains. The stable Pt (110) facets of the nanoplates have high ORR specific and mass activities that reach 7.8 milliampere (mA) per centimeter squared and 4.3 ampere per milligram of platinum at 0.9 volts versus the reversible hydrogen electrode (RHE), respectively. Density functional theory calculations reveal that the edge-Pt and top (bottom)-Pt (110) facets undergo large tensile strains that help optimize the Pt-O bond strength. The intermetallic core and uniform four layers of Pt shell of the PtPb/Pt nanoplates appear to underlie the high endurance of these catalysts, which can undergo 50,000 voltage cycles with negligible activity decay and no apparent structure and composition changes.

Nanocrystalline metallic materials have the merit of high strength but usually suffer from poor ductility and rapid grain coarsening, limiting their practical application. Here, we introduce a core-shell nanostructure in a multicomponent alloy to address these challenges simultaneously, achieving a high tensile strength of 2.65 GPa, a large uniform elongation of 17%, and a high thermal stability of 1173 K. Our strategy relies on an ordered superlattice structure that excels in dislocation accumulation, encased by a ≈3 nm disordered face-centered-cubic nanolayer acting as dislocation sources. The ordered superlattice with high anti-phase boundary energy retards dislocation motions, promoting their interaction and storage within the nanograins. The disordered interfacial nanolayer promotes dislocation emission and effectively accommodates the plastic strain at grain boundaries, preventing intergranular cracking. Consequently, the order-disorder core-shell nanostructure exhibits enhanced work-hardening capability and large ductility. Moreover, such core-shell nanostructure exhibits high coarsening resistance at elevated temperatures, enabling it high thermal stability. Such a design strategy holds promise for developing high-performance materials. Nanocrystalline metallic materials have the merit of high strength, but usually suffer from poor ductility and rapid grain coarsening. Here, the authors develop a nanocrystalline core-shell alloy to overcome these challenges.

For alloys displaying diffusive transport behaviour, understanding the electrochemical factors that control dealloying-induced morphologies could prove important for battery development. Composition, particle size and dealloying rate are now shown to affect morphology evolution in the Li–Sn system, and dealloying is found to be governed by both percolation-dissolution and solid-state-diffusion mechanisms. Dealloying, the selective dissolution of one or more of the elemental components of an alloy, is an important corrosion mechanism and a technologically relevant process used to fabricate nanoporous metals for a variety of applications including catalysis 1 , sensing 2 , actuation 3 , supercapacitors 4 and radiation-damage-resistant materials 5 . In noble-metal alloy systems for which the ambient-temperature solid-state diffusivity is minuscule, dealloying occurs at a composition-dependent critical potential above which bicontinuous nanoporous structures evolve and below which a full-coverage layer of the more-noble component forms causing the alloy surface to become passive 6 , 7 . In contrast, for alloy systems exhibiting significant solid-state diffusive transport, our understanding of dealloying-induced morphologies and the electrochemical parameters controlling this are largely unexplored. Here, we examine dealloying of Li from Li–Sn alloys and show that depending on alloy composition, particle size and dealloying rate, all known dealloyed morphologies evolve including bicontinuous nanoporous structures and hollow core–shell particles. Furthermore, we elucidate the role of bulk diffusion in morphology evolution using chronopotentiometry and linear sweep voltammetry. Our results may have implications for lithium-ion battery development while significantly broadening the spectrum of strategies for obtaining new nanoporous materials through dealloying.

Water-soluble Ag-Au bimetallic nanostructures were prepared via co-reduction and seed-mediated growth routes employing poly-(4-styrenesulfonic acid-co-maleic acid) (PSSMA) as both a reductant and a stabilizer. Ag-Au alloy nanoparticles were obtained by the co-reduction of AgNO 3 and HAuCl 4 , while Ag-Au core-shell nanostructures were prepared through seed-mediated growth using PSSMA-Au nanoparticle seeds in a heated AgNO 3 solution. The optical properties of the Ag-Au alloy and core-shell nanostructures were studied, and the growth mechanism of the bimetallic nanoparticles was investigated. Plasmon resonance bands in the range 422 to 517 nm were observed for Ag-Au alloy nanoparticles, while two plasmon resonances were found in the Ag-Au core-shell nanostructures. Furthermore, discrete dipole approximation theoretical simulation was used to assess the optical property differences between the Ag-Au alloy and core-shell nanostructures. Composition and morphology studies confirmed that the synthesized materials were Ag-Au bimetallic nanostructures.

Achieving stable surface structures of metal catalysts is an extreme challenge for obtaining long-term durability and meeting industrial application requirements. We report a new class of metal catalyst, Pt-rich PtCu heteroatom subnanoclusters epitaxially grown on an octahedral PtCu alloy/Pt skin matrix (PtCu 1.60 ), for the oxygen reduction reaction (ORR) in an acid electrolyte. The PtCu 1.60 /C exhibits an 8.9-fold enhanced mass activity (1.42 A·mg Pt −1 ) over that of commercial Pt/C (0.16 A·mg Pt −1 ). The PtCu 1.60 /C exhibits 140,000 cycles durability without activity decline and surface PtCu cluster stability owing to unique structure derived from the matrix and epitaxial growth pattern, which effectively prevents the agglomeration of clusters and loss of near-surface active sites. Structure characterization and theoretical calculations confirm that Pt-rich PtCu clusters favor ORR activity and thermodynamic stability. In room-temperature polymer electrolyte membrane fuel cells, the PtCu 1.60 /C shows enhanced performance and delivers a power density of 154.1/318.8 mW·cm −2 and 100 h/50 h durability without current density decay in an air/O 2 feedstock.

The improvement of catalysts for the oxygen-reduction reaction is an important challenge for fuel cells and other electrochemical-energy technologies. A composite nanoporous Ni–Pt alloy with a tailored geometric architecture is now shown to exhibit high mass activity for oxygen reduction. The improvement of catalysts for the four-electron oxygen-reduction reaction (ORR; O 2 +4H + +4e − →2H 2 O) remains a critical challenge for fuel cells and other electrochemical-energy technologies. Recent attention in this area has centred on the development of metal alloys with nanostructured compositional gradients (for example, core–shell structure) that exhibit higher activity than supported Pt nanoparticles (Pt–C; refs  1 , 2 , 3 , 4 , 5 , 6 , 7 ). For instance, with a Pt outer surface and Ni-rich second atomic layer, Pt 3 Ni(111) is one of the most active surfaces for the ORR (ref.  8 ), owing to a shift in the d -band centre of the surface Pt atoms that results in a weakened interaction between Pt and intermediate oxide species, freeing more active sites for O 2 adsorption 2 , 9 . However, enhancements due solely to alloy structure and composition may not be sufficient to reduce the mass activity enough to satisfy the requirements for fuel-cell commercialization 10 , especially as the high activity of particular crystal surface facets may not easily translate to polyfaceted particles. Here we show that a tailored geometric and chemical materials architecture can further improve ORR catalysis by demonstrating that a composite nanoporous Ni–Pt alloy impregnated with a hydrophobic, high-oxygen-solubility and protic ionic liquid has extremely high mass activity. The results are consistent with an engineered chemical bias within a catalytically active nanoporous framework that pushes the ORR towards completion.

Hydrogen peroxide (H2O2) plays important roles in cellular signaling and in industry. Thus, the accurate detection of H2O2 is critical for its application. Unfortunately, the direct detection of H2O2 by surface-enhanced Raman spectroscopy (SERS) is not possible because of its low Raman cross section. Therefore, the detection of H2O2 via the presence of an intermediary such as 3,3,5,5-tetramethylbenzidine (TMB) has recently been developed. In this study, the peroxidase-mimicking activity of gold–silver core–shell-assembled silica nanostructures (SiO2@Au@Ag alloy NPs) in the presence of TMB was investigated using SERS for detecting H2O2. In the presence of H2O2, the SiO2@Au@Ag alloy catalyzed the conversion of TMB to oxidized TMB, which was absorbed onto the surface of the SiO2@Au@Ag alloy. The SERS characteristics of the alloy in the TMB–H2O2 mixture were investigated. The evaluation of the SERS band to determine the H2O2 level utilized the SERS intensity of oxidized TMB bands. Moreover, the optimal conditions for H2O2 detection using SiO2@Au@Ag alloy included incubating 20 µg/mL SiO2@Au@Ag alloy NPs with 0.8 mM TMB for 15 min and measuring the Raman signal at 400 µg/mL SiO2@Au@Ag alloy NPs.

Nowadays, numerous works regarding nanowires or nanotubes are being published, studying different combinations of materials or geometries with single or multiple layers. However, works, where both nanotube and nanowires are forming complex structures, are scarcer due to the underlying difficulties that their fabrication and characterization entail. Among the specific applications for these nanostructures that can be used in sensing or high-density magnetic data storage devices, there are the fields of photonics or spintronics. To achieve further improvements in these research fields, a complete understanding of the magnetic properties exhibited by these nanostructures is needed, including their magnetization reversal processes and control of the magnetic domain walls. In order to gain a deeper insight into this topic, complex systems are being fabricated by altering their dimensions or composition. In this work, a successful process flow for the additive fabrication of core/shell nanowires arrays is developed. The core/shell nanostructures fabricated here consist of a magnetic nanowire nucleus (Fe56Co44), grown by electrodeposition and coated by a non-magnetic SiO2 layer coaxially surrounded by a magnetic Fe3O4 nanotubular coating both fabricated by means of the Atomic Layer Deposition (ALD) technique. Moreover, the magnetization reversal processes of these coaxial nanostructures and the magnetostatic interactions between the two magnetic components are investigated by means of standard magnetometry and First Order Reversal Curve methodology. From this study, a two-step magnetization reversal of the core/shell bimagnetic nanostructure is inferred, which is also corroborated by the hysteresis loops of individual core/shell nanostructures measured by Kerr effect-based magnetometer.

Au-Ag alloy nanostructures with various shapes were synthesized using a successive reduction method in this study. By means of galvanic replacement, twined Ag nanoparticles (NPs) and single-crystalline Ag nanowires (NWs) were adopted as templates, respectively, and alloyed with the same amount of Au+ ions. High angle annular dark field-scanning TEM (HAADF-STEM) images observed from different rotation angles confirm that Ag NPs turned into AuAg alloy rings with an Au/Ag ratio of 1. The shifts of surface plasmon resonance and chemical composition reveal the evolution of the alloy ring formation. On the other hand, single-crystalline Ag NWs became Ag@AuAg core-shell wires instead of hollow nanostructure through a process of galvanic replacement. It is proposed that in addition to the ratio of Ag templates and Au ion additives, the twin boundaries of the Ag templates were the dominating factor causing hollow alloy nanostructures.